Process for breaking petroleum emulsions employing certain oxyalkylated acyclic diglycerols



y 12, 1 M. DE GROOTE ETAI. 2,944,982

PROCESS FOR BREAKING PETROLEUM EMULSIONS EMPLOYING CERTAIN OXYALKYLATED ACYCLIC DIGLYCEROLS Filed June 10, 1954 BUTYLENE OXIDE I00% ACYCLIC DIGLYCEROL ETHYIIENl-E !00 OXIDE I00 4 INVENTORS el t t Patsfl PROCESS FOR BREAKING PETROLEUIVI EMUL- SIONS EMPLOYING CERTAIN OXYALKYLATED ACYCLIC DIGLYCEROLS Melvin Decroote, University City, and Owen H. Pet-' tingill, Kirkwood, Mo., ,assignors to Petrolite Corporation, Wilmington, DeL, a corporation of Delaware Filed June 10, 19s4,ser.No. 435,663

20 Claims crass-s31 invention relatesto processes or procedures particularly adapted for preventing, breaking or resolving emulsions of thewater-in-oil type, and particularly petroleum. emulsions. x o r Our invention provides an economical and .rapid processfor resolving cpetroleum femulsions of the water-in-t oiltype "that are commonly referred. to as cut on," roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of theemulsion.

It also provides'an economical and rapid process for' separating emulsions which have been prepared under controlled conditions from mrl'deral oil, such as'cr' ude oil and relatively soft waters or weak brines. Controlled glycerol. The cogeneric mixture is derived exclusively from acyclic diglycerol, ethylene oxide andbutylene oxide in such weight proportions so the average composition of said cogeneric mixture statedin terms of in itial reactants lies approximately within the 5 -si,dcd figure of the accompanying drawing in which the minimum acyclic diglycerol content is at least 1.5% and which 5-sidedfigur'e is identified by thefact that its area lies within. the straight lines connecting A, B, C, D, and H.

All references to diglycerol, unless the text indicates con-,-

trariwise, means acyclic diglycelrol having 4 hydroxyl radicals.

We have, found that when (ii glycerol is v combinedwith butyleneoxide and ethylene oxide incertain proportions and particularly when the butylene oxide is employed first, followed by use of ethylene oxide and morefespecially if the butylene oxide employed is one of the straightchain isomers or a mixture of the two audit the composition falls with-- in thelimits indicated by the S-sided figure on the hereto attached triangular chart, said derivatives are of unusual eifectiveness for a number of purposes particularly when surface activity, is a factor,

tion of petroleum emulsions of the water-in-oil type.

been treated with about 11 to.39 parts of butylene oxide, by weight, and then reacted with 27 to 58.5 parts of ethylene oxide. I w V V In another series 10 parts of diglycerol have been reacted with 5 parts by weight of butylene oxide and parts by weight of ethyene oxide. In anotherseries 1.5 parts by weight of diglycerol have been reacted with 13.5 parts-by Weight of butylene oxide and 85 parts by weight of ethylene oxide. Similarly, in another series the following combinations have been 'used: 1.5 parts of diglycerol combined with 58.5'partsby weight of butylene oxide and 40 parts by weight of ethylene oxide; 20 parts by weight of diglycerol, reactedwith 40 parts by weight of butylene' oxide and then with 40 partsby weight of ethylene oxide! In another series 20 parts by weightof .diglycerol were reacted with 10 parts by weight of butylene oxide and then 70 parts byweight of ethylene oxide. f

it is of interest ,to note in some instances asflittle" as 1. S parts of diglycerol may be combined with 9815 parts of-the two oxides to produce very valuable deriv-.j

atives.

' We have alsofound that where part of the butylene oxide is replaced by propyleneoxide, i.e., where' acorn bination of diglycerol, butyle'ne oxide, .propylenei'oxide and ethylene oxide are used, efiectiveand valuable sur- This, "however,

least the test set forth in US. PatentfNof 2,499,368,

dated March 7, 1950, to De Groote and Keiser. V In said patent such test for emulsification using a water-insola uble solvent, generally xylene, is described as an index ofsurface activity. on p a The above mentioned test, i.e., a conventional emulsification test, simply means that the preferred product. for deniulsification is soluble in a solvent having hydro phobe properties or in an oxygenated water insoluble or even a fraction of a water-soluble hydrocarbon solvent or even a \fraction of a water-soluble hydrocarbon .solvent and that when shaken with waterthe product may remainxin the nonaqueous solvent or, 'for that matter it may pass into the aqueous solvent. .In other words, al-) though it is xylene soluble, for'example, .it' may also be water soluble to an equal'or greater degree.

For will be divided into three parts:

Part 1 is concerned with the oxyalkylation of diglycerol in general; a 7

Part 2 is concerned with the oxyalkylation of diglycerol using two difierent oxides, i.e., butylene oxide and ethylene oxide so as to produce derivatives falling within certain composition limitations hereinafter noted in detail. For convenience, Part 2 is divided into two sections, Section A is concerned with oxybutylation and oxyethylation broadly, and Section Bis concerned with the particular compositions corresponding to the herein specified compositions and illustrate such combinations;.-

Part 3 is concerned "with the resolution of petroleum Pa e t either directly or indirectly. One example-is the use of such derivatives in the 'r esolupurpose of convenience what issaid .hereinafte emulsions of the water-in-oil type by means of the previously described chemical compounds.

PART 1 At the present time there is available butylene oxide which includes isomeric mixtures, for instance, one manufacturer has previously supplied a mixed butylene oxide which is in essence a mixture of l-butene oxide, 2-butene oxide isomers and approximately isobutylene oxide. Another manufacturer has supplied an oxide which is roughly a fifty-fifty mixture of the cisand trans-isomers of 2-butene oxide.

There is also available a butylene oxide which is characterized as straight chain isomers being a mixture of the 1,2 and the 2,3 isomers and substantially free from the isobutylene oxide.

This latter product appears to consist of 80% of the 1,2 isomer and of the mixed 2,3 cisand 2,3 transisomer. We have obtained the best results by using an oxide that is roughly 80% or more of the 1,2 isomer and with either none, or just a few percent if any, of the isobutylene oxide, the difference being either form of the 2,3 or a mixture of the two forms.

Our preference is to use an oxide substantially free from the isobutylene oxide, or at least having minimum amounts of isobutylene oxide present.

Since the varying solubility of different butanols is well known, it is unnecessary to comment on the effect that the varying structure has on solubility of derivatives obtained by butylene oxide. Purely by way of example, the applicants have tested the solubility of the first two available butylene oxides and noted in one instance the butylene oxide would dissolve to the extent of 23 grams in 100 grams of water, whereas the other butylene oxide would only dissolve to the extent of 6 grams in 100 grams of water. These tests were made at 25 C.

As to further reference in regard to the isomeric butylene oxides see Chemistry of Carbon Compounds, volume 1, part A, Aliphatic Compounds," edited by E. H. Rod-d, Elsevier Publishing Company, New York, 1951, page 671.

As to the dilference in certain proportions of the cisand trans-form of straight chain isomers 2,3-ep0xybutane see page 341 of A Manual of Organic Chemistry, volume 1, G. Malcolm Dyson, Longmans, Green and Company, New York, 1950.

Reference to butylene oxide herein of course is to the compound or compounds having the oxirane ring and thus excludes 1,4-butylene oxide (tetrahydrofurane) or a trimethylene ring compound.

When reference is made to the oxides, for instance, ethylene oxide and butylene oxide, one can use the corresponding carbonates. Ethylene carbonate is available commercially. Butylene carbonate, or the carbonate corresponding to a particular oxide, is not avilable commercially but can be prepared by the usual methods in the laboratory. For this reason further reference to the.

alkylene carbonates will be ignored although it is, understood when oxyethylation takes place by means of ethylene carbonate one could, of course, use butylene carbonate for oxybutylation.

In the present invention we have found that outstanding products are obtained by the use of certain preferred butylene oxides, i.e., those entirely free or substantially free (usually 1% or less) and composed of approximately 85% or more of the 1,2 isomer with the remainder, if any, being the 2,3 isomer.

In the preparation of the outstanding compounds we have studiously avoided the presence of the isobutylene oxide as far as practical. When any significant amount of isobutylene oxide happens to be present, the results are not as satisfactory regardless of the point when the butylene oxide is introduced. One explanation may be the following. The initial oxybutylation which may be simplified by reference to a monohydric alcohol, produces a a tertiary alcohol. Thus the oxybutylation in the presence of an alkaline catalyst may be shown thus:

Further oxyalkylation becomes difficult when a tertiary alcohol is involved although the literature records successful oxyalkylation of tertiary alcohols. This does not necessarily apply when oxyalkylation takes place in the presence of an acidic catalyst, for instance, a metallic chloride such as ferric chloride, stannic chloride, aluminum chloride, etc.

The difliculty is that there is some tendency on the part of digylcerol to convert to a higher polyglycerol such as the tetraglycerol or form acyclic compounds in which hydroxyl groups are lost. If one proceeds under such circumstances one would be oxyalkylating not only acylic diglycerol but possibly cyclic triglycerol to say nothing of higher polyglycerols such as tetraglycerols (cyclic or non-cyclic) and water. We have tried procedures using an alkaline catalyst and diglycerol employing 4 to 6 moles of isobutylene oxide per mole of diglycerol. Afterwards an amount of acid was added equal to the amount of caustic employed as a catalyst and the reaction mass dried and then stannic chloride added. Under such circumstances results suggest more satisfactory oxybutylation as such although the procedure becomes cumbersome, uneconomical, and perhaps even impractical.

This, however, seems to be only a partial explanation. Another explanation may rest with the fact that isobutylene oxide may show a tendency to revert back to isobutylene and oxygen and this oxygen may tend to oxidize the terminal hydroxyl radicals. This possibility is purely a matter of speculation, but may account for the reason we obtain much better results using a butylene oxide as specified. In regard to this reaction, i.e., possible conversion of an alkylene oxide back to the olefine and nascent oxygen, see Tall Oil Studies II, Decolorization of Polyethenoxy Tallates With Ozone and Hydrogen Peroxide, J. V. Karabinos et al.,-I. Am. Oil Chem. Soc. 31, 71 (1954).

In order to illustrate why the herein contemplated compounds or said products are cogeneric mixtures and not single chemical compounds, and why they must be described in terms of manufacture, and molal ratio or percentage ratio of reactants, reference is made to a monohydric alcohol. Diglycerol, of course, is a polyhydric alcohol having 4 hydroxyls. However, one need only consider what happens when a monohydric alcohol is subjected to oxyalkylation.

If one selects any hydroxylated compound and subjects such compound to: oxyalkylation, such as oxyethylation, it' becomes obvious that one is really producing a polymer of the alkylene oxide except for the terminal group. Thisisfparticularly true where the amount of oxide added is comparatively large, for instance, 10, 20,

30, 40, or 50 units. If such a compound is subjected to oxyethylation so as to introduce units of ethylene oxide, it is well known that one does not obtain a single constituent which, for sake of convenience, may be indicated a RO( C H O) I-I. Instead, one obtains a cogeneric mixture of closely relates homologues in which the formula may be shown as the following:

RO(C H O),,H

wherein n, as far as the statistical average goes, is 30, but the individual members present in significant amount may vary from instances where n has a value of 25 and 75 perhaps less, to a point where 11 may represent or alkylation.

aeiisi more; mixture is', as stated, a cogeneric closely,

related series of touchin'ghomologous compounds, C9 17 siderable investigation has been made in regar to. t e;

distribution curves for'linear'po lymers Attention is directed, to the article entitled Fundamental Principlesof Condensation Polymerization, by'Paul I. Flory, which appeared in Chemical Reviews, yolume 39, No. 1, page 137. r

Unfortunately, as has fbcen'rtrpointed out by Flory and other investigatorgthereds no s tisit'actory method based a l thsr x i ent r me a en. q a in frt vqrt cn condensation products ot thekind described." that from the practicall standpoint, re, th A describe how to make the p'rodi1ct under consideration and how to repeat such production time after time with} out difliculty it is necessary to resort to some other mthodof description. 'f '1 What has been said in regard 'to a monohydric conipoundof course is multiplied many 'timesin the case of a tetrahydric compound such as digtlycerol. This is particularly true even in regard to ethyleneoxide alone but becomes even more complicated when butylene oxide is used in light of what has been said previously in regard to the isomers of butylene oxide.

'P nT 2 Section A V The oxyalkylation of glycerol or polyglycerol, including acyclic diglycerol, has been described in the literature.

The procedure is the same as the oxyalkylationof ethyl ene -glycol, propylene glycol; butylene glycol or the like.

. v h a i u mwb r of touching homologous series which appearincog eric;

parts by weight of butylene oxide toonepart of diglycerol.v The xylenepresent represented approximately .6 of one part by weight.

i l i Example 2a Th r a lm w st ans fl m t a sera it v (s aci ygfi e s). iYY hg tnadd a o lvent.

or anyfmore xylene the procedure'was repeated so as to.

add another 1500 grams of butylene oxide under substan'{ tially the same operating condi tiqns but requiring about 2% hoursfor the addition. "At the end of this step ;the rati' representedapproximately 6 to 1 (ratio butylene QXidfiJQ ig y flm lt t v Example 3a In a third s tep in'stead of-adding 1500 grams of'but ylene oxide, 1625 grams were added. Thereaction slowed up and required approximately hours, using the same operating temperatures "and pressures. The ratio at the Instead, no particular problem is involved because the product is a liquid at 'oxyalkylation. temperatures, for-instance, 120. C.-to 130 C. J p 1 a 7 Purely as a matter of convenience it is not unusual to add a solvent,such as xylene, which-only'forms a suspension or emulsion with diglycerol. when agitationis employed. ,However, as soon as the product becomes oxybutylated or oxypropylated to anydegree the reaction massis xylene-soluble andithus thereis some benefit by the reduction in viscosity of the reaction mass. We have employed xylene although it isv not necessary and may be omitted if desired. It is purely a convenience in oxy- Itjis not 'believed any examples are necessary to illustrate such well known procedure butfor purpose of illustration the following are included:

I I Exampl'Ja 5 p c The reaction vessel employed was, a stainless steel autoclave with the usual devices for, heating, heat control, stirrer, inlet, outlet, etc., which is conventional in this type of apparatus. The capacity was approximately 4 liters. I The stirrer operated at a speedof approximately 250 'r.-p.m. There were charged'irito the autoclave 500' end of the third step was 925 parts by weight of butylene oxide per'weight of diglycerol.

Example 4a At the end of this step the autoclave was'opened and an additional 5 grams "of sodium methylate' added, the autoclave flushed out as before, and the fourth and final oxyalkylation completed, using 1625 grams of butylene oxide, and the oxyalkylation was complete within 3 hours using the same temperature range and pressure as previously. At the end of the reaction the product represented approximately 12.5 parts of butylene oxide by weight to one part of diglycerol.

All the examples, except the first step, were substantially water-insoluble and xylene-soluble.

MAs'hasbeen pointed out previously these oxybutylated diglycerols were subjectedto oxyethylation in the same manner. described in respect to the oxybutylated digly- I cerol; Indeed, the procedure is comparatively simple for the. reason that one isWOrking with a liquid and also that ethylene oxide is more reactive than butylene oxide. As

a result,.using the same amount of catalyst one can oxyethylate more rapidly than usually at a lower pressure.

There is no substantial difference as far as operating procedure goes Whether one is oxyethylated digly'cerol or oxybutylated diglycerol.

Thesame procedure using a slurry of finely powdered diglycerol in xylene was employed in connection with W ethylene oxide and the same mixture on a percentage basis was obtained as in the above examples where butylene oxide'and. diglycerol were used.

The same procedures have been employed using other butyleneoxides including mixtures having considerable -isobutylene oxide and mixtures of the straight chain -isomers with greater or lesser amounts of the 2,3 isomer.

grams'of diglycerol, 300 grams of xylene,and .15 grams a of sodium niethylate. The autoclave was sealed-sweptwith nitrogen gas and stirring started immediately and; e temperature was allowedto rise to approximately .14? C. At this particulartime the addir; tionpf butylene oxide was started; The butylene-oxide. employed-was .amixture of the straight chain isomersub stantiallytreeijfrom isobutyleneioxide It was addedcom,

l tinuously at such speed that it was absorbed by the reaction 'as added. The amount added in this operation was heat applied; 4

1500 grams; The time required to add the butylene oxide and then the other.

was 1% hours; During this period the temperatureuwas' l maintained at 130 to 145 C., using cooling water applying heatif required. The maximum pressure during the. reaction 47 pounds per squareinch. Ignoring the X e e dsdi mm h ste n .s n r e diglycw erol for convenience, the resultant product represents 3 through the inner coils when necessary and otherwise.

Where reference has been made in previous examples to the straight chamisomer, the product used fwas one which wasv roughly 85% or more of the 1,2'isomer andapproximately' 15%-of the 2,3-cisandqthe *2,-3-trans- 1 isomerwith substantially none or not over- 1%, of'the,

as a matter of fact, we have used such methods in connection with molten sorbitol. I i: H W If desired, one may and part of one oxide and all ot:

"'5 the other and then return to the use of the firstoxide,

for instance; or one may use the procedure as previously,

' be added in portions so that firstzone oxide is added, then the other, then the first oxide is added again, and then the s'econd oxide. We have 'found no advantage in so doing. Indeed, our preference has been to add all the butylene oxide first and then the required amount'of ethylene oxide. t

As "pointed out previously,diglycerolcan be oxyethylated in the same way 'it is oxybutylated, i.e., by preparing a slurry in xylene orin'a siriiilar'solventfand using a suitable alkaline catalyst such as caustic soda, sodium methylate, or the like, and then adding the ethylene oxide. The changes previously mentioned are of difference in degree only. In other words, oxyethylation will take place at a lower temperature, for instance, a top temperature of probably 130 to 135 C. instead of 145 to 150 C. The same weight of ethylene oxide could be added in 75% to 85% of the time required for. butylene oxide. The pressure during the reaction, instead of being 35 to 45 pounds as in the case of butylene oxide, is apt to be to pounds and at times a little higher. Otherwise, there is no difference.

trace of moisture. Our preference is to prepare the slurry with an excess of xylene and distill 01f a part of the out the "mass nitrogen. Even so,' th'ere may be a fewtenths of a percentcfmoistureremain although at times ex'aifriination indicates at the 'rrio's't it is merely a trace. 5 I

' PART 2 Secti0'n'B In light of'what has been said "previously, particularly Section A, it is obvious that hardly any directions are .to produce the compounds herein specified. However, referring to the composition of the initial reactants; based on the S-sided figure in the attached drawing, it will be noted we have calculated the percentage of the three initial reactants for the points A, B, C, D,

E, F, G, H, I and I which appear on the boundary of. the S-sided figure and also determine t-he five sub-divided parts of theS-Sided figure, two parts being triangles and i the others being two parallelograms and one trapezoid.-

Likewise, we have calculated the composition for a nurn berof examples within the area of the-graph andcorresponding to points 1 to 18, inclusive. Note these data are included in Table I, immediately following:v

TABLE I Tertiary Mixture, Binary Intermediate Mixtures,

Percent Basis Percent Basis Points on Boundary of Area Acycllc Butyl- Ethyl- Acyclic Butyl- Acyclic Ethyl- Dlene ene Diene Diene glycerol Oxide Oxide glycerol Oxide glycerol 7 Oxide 10.0 5. 0 85.0 66. 6 33. 4 10. 5 89. 5 1. 5 13. 5 85.0 10.0 90. 0 1. 7 98. 3 1. 5 58. 5 40.0 2. 5 97. 5 3.6 96.4 Y 20.0 40.0 40. 0 38. 4 66. 6 33. 4 66. 6 1. 5 40. 0 58. 5 3. 6 96. 4 2. 5 97. 5 1. 5 30.0 68. 5 4t 75 95. 2.14 97. 86 1. 5 20.0 78. 5 7.0 93. 0 1. 87 98.13 20.0 10.0 70.0 66. 6 33. 4 22. 2 77. 8 20.0 20.0 60.0 50.0 50.0 25.0 75.0 20.0 30.0 50.0 40.0 60.0 28.6 71. 4 5.0 52. 5 42. 5 8. 68 91. 32 10.5 89. 5 8.0 44.0 48. 0 15. 4 84. 5 l4. 3 85. 7 1. 5 54. 5 44. 0 2. 68 97.32 3.3 96. 7 18.0 36. 5 45. 5 33. 0 67.0 28. 3 71. 7 15.0 33. 5 51. 5 31.0 69. 0 22. 6 77.4 7. 5 36. 5 56.0 17. 1 82. 9 11. 8 88. 2 1. 5 34. 5 64. 0 4.16 95. 84 2. 3 97.7 17. 0 28.0 55.0 37. 7 62. 3 23. 6 76. 4 7.0 26.0 67.0 21. 2 78. 8 9. 5 90. 5 13. 5 22. 5 64. 0 37. 5 62. 5 17. 4 82.6 15.5 19.0 65. 5 44. 8 55. 2 19.2 80. 8

Also, if desired, the use of ethylene carbonate is a very convenient way of oxyethylating diglycerol. In fact, it can be oxyethylatedwithout the use of pressure. Such procedure, and particularly melting the carbonatefirst and adding the powdered diglycerol slowly permits the production of a' reaction mass which is a 'liquid'or which melts readily at comparatively low temperatures to yield a liquid. Such reaction should be conducted in such a way that there is no residual ethylene carbonate when the mass is transferred to an autoclave.

One can oxyalkylate using an acid catalyst or an alkaline catalyst or at least in part, without the use of any catalyst although such procedure is extremely slow and uneconomical. In other words, any one of the conventionalcatalysts used in oxyalkylation may be employed. It is our preference, however, to'use an alkaline catalyst such as sodium methylate, caustic soda, orthe like.

Actually; vfiliely Pbwdfe'd dig y may contain a ouspoints onthe boundary and within the 5-sided figure propriate number of pounds of oxide; for instance, in

regard to point A all that would be necessary would be to mix 5 pounds of butylene oxide with pounds of ethylene oxide and use the mixture to oxyalkylate 10 pounds of diglycerol.

Similarly, in Example B, one need only mix 13.5

0 pounds of butylene oxide with 85 pounds of ethylene oxide and use the mixture to oxyalkylate 1.5 pounds of diglycerol in the manner previously indicated.

Note the fifth and sixth columns represent binary intermediate mixtures. For instance, in regard to the vari- Thus it is apparent that one ene.

flied, we have calculated'the initial mixture using glycerol and butylene oxide in the first case, "and using diglycerol and ethylene oxide in the second case, which would be employed for subsequent oxyal-kylation to give the particular composition required. Note that a binary. intermediate for the preparation of point A can be pre-. paredany suitable manner involving 66.6% of diglyc-i erol and 33.4% of butylene oxide. Thus, for example one could use 66.6-pounds of diglycerol and 33.4pounds of butylene oxide, or on a larger scale one could use 666'pounds of diglycerol and 334 pounds of butylene oxide. i "i 1 Referring now to the tertiary mixture table, it is ap-; parent that for point A diglycerol and butylene oxide together represent 15 and ethylene oxide 85%. Therefore, one could employ ,15 pounds of the binary mixture and react it with 85pounds ofethylene oxide. I

Similarly, in regard to the fifth and sixthcolumns for point B, the initial mixture involved diglycerol and butylenef'oxide, representing 10% of diglycerol, and 90% of butyleneoxide. i If desired; 10 pounds of diglycerol could be? reacted with 90 pounds of butylene oxide. Such mixture needionly be reacted with ethylene oxide by re- 1 acting ,15 pounds of the mixture with 85 pounds of ethyl- This is obvious from the data in regardto the tertiarymixtures. a 1 L1,. 1

:1 Referrihg now to columns 7and 8, it is obyious one could readily produce an oxyethylated diglycerol and then subject it toreaction with butylene oxide; --Using this procedure inregard to A, it is obvious that the mixture represents 10.5% of diglycerol and 89.5% of ethyleneoXi deiL-This product could be obtained from a binary mixture of 105 pounds of' diglycerol and 895 pounds of ethylene oxide. I

:uerer ng-now to the tertiary mixture table, {it is-ob- V vious-that 95 pounds of'such mixture could'be reacted with 5 pounds of butylene oxide to give point A. :Simi-'' larly, in regard 'to point'B theoxye thylated diglycerol represents 1.7% of diglycerol and 98.3 ethylene oxide. The mixture so obtained by referring to the tertiary mix ture tablewouldbe-reactedwith butylene oxide in.the proportion of 86.5 pounds of the mixture and 13.5 pounds of butylene oxidenj 7f ,Aspreviously pointed out, the oxyalkylationof diglyc erol has" been described inthe literature and is de-l TABLE II Composition Composition Composition where Butylwhere' Ethyl- Composltion Corresponding where, Oxides ene Oxide -ene Oxide' to Following Point are Mixed Used First Used First Prior to Oxy- Followed by Followed by alkylation Ethylene Butylene Oxide Oxide A Aa Ab Ac B Ba Bb Be Ca Cb Cc D Da Db Dc E- Ea Eb Ec F Fa Fb Fa G Ga Gb Gc H Ha Hb Hc I- Ia Ib I0 I. lo J1: J0 1a 1b 1c 2- 2a 2b 2c 3. 3a 3b 3c 4a 4b 4c 5 5a 5b 5c 6a 6b 6c 7a 7b 7c 8a 8b 86 9a 9b 9c 10a 10b 100 11a 11b 11c 12a 12b 120 13a 13b 131: 14a 14b 140 15a 15b 150 16a 16b 16c 17a 17b 17a 18a 18b 18c inabove... All on'e'need do is employ such conventional oxyalkylation procedure to obtain products corresponding to the compositions as defined. :At- 3 tention is; again directed to the fact that one need notadd the entire amountof either oxide atone time but that asmall' portion of one could be added and then another.

small portionof the other, and the process repeated.

butylene oxides and ethylene oxide were mixed; this series isindicatedasAa, Ba, through and including 18a; in the second series butylene voxide was used first followed -rby ethylene oxide and this series indicated Ab, Eb,

through and including 18b; and finally in the third series ethylene oxide was used followed by butylene oxide and the series identified as Ac, Bc, through and including 18C.

-:The products obtained by the above procedure usually .show some color varying from a light amber to a pale straw. They can be bleached in the usual fashion using bleaching clays, charcoal, or an organic bleach, such as peroxide or peracetic acid, or the like.

. Such products also have present a small amount of alkaline catalyst which can be removed by conventional means,'"or...they can be neutralizedby adding an equivalent amount-of .acid, such as hydrochloricacid'. :For

many purposes the slightamountof residual alkalinity is not objectionable. V

There are certain variants which can be employed without detractingxfroin the .metes and bounds of the invention, but for'all practical purposes there is nothing to be gained by. such variants and the result is merely increased cost; For instance, any one of the two oxides can be replaced to a minor percentage and usually to a very small degree, by oxide which would introduce substantially the same; group along with aside chain, for I instance, one could employ glycidyl methyl ether, glycidyl ethyl ether,;glycidyl isopropyl ether, glycidyl butyl ether or. the likeJ-"c;

Increasedbranching also may be effected by the use of animine instead of a glycide, or a methyl glycide.

Thus onefcan useethylene imine, or propylene imine in thesame' wa described for glycide or methyl glycide. An additional efiectis obtained due to the basicity of the ,nitrogenatorn. The same thing is true as far as the inclusion of nitrogen atoms if one uses a compound of the kind previously describedsuch as 'a dialkylaminoepoxypropane; Excellent products areobtained by reacting diglycerol with one to six moles of ethylene' irnine and then proceeding in the same manner herein described.

11111] the hereto appended claims reference. has been made to glycol ethers of diglycerol. Actually it well may be that the products should be referred to as polyol ethers or diglycero in order to emphasize the fact that the final products of reaction have more than two hydroxyl radicals. However, the products may be considered as hypothetically derived by reaction'of diglycerol with the glycols, such as ethylene glycol, butylene glycol, propylene glycol, or polyglycols. For this reason there seems to be a preference to use the terminology'glycol ethers of diglycerol.

PART 3 As to the use of conventional demulsifying agents, reference is made to U.S. Patent No. 2,626,929, dated January 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and efiect to the instant process, noting only that where reference is made to Example 13b in said text beginning in. column 15 and ending in column 18, reference should be to Example 18b, herein described. I

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A process for breaking petroleum emulsions of the water-in-oil type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers of acyclic diglycerol; said cogeneric mixture being derived exclusively from acyclic diglycerol, ethylene oxide and butylene oxide in such weight proportions so the average composition of said cogeneric mixture, stated in terms of initial reactants, lies approximately Within the S-Sided figure of the accompanying drawing in which the minimum acyclic diglycerol content is at least 1.5% and which S-sided figure is identified by the fact that its area lies within the straight lines connecting A, B, C, D, and H.

2. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

3. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

4. Theprocess of claim 1 with the proviso that oxya-lkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the-butylene oxide is substantially free from isobutylene oxide.

5. The process of claim 1 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of 85% or more of the 1,2-isomer and approximately 15% or less of the 2,3-isomeric form, and is substantially free from isobutylene oxide.

- 6. The process of claim with the proviso that the reactant composition falls within the triangular area defined by C, D, and E.

' 7. The process of claim 5 with the proviso that the reactant composition falls within the parallelogram D, E, F, and J.

8. The process of claim 5 with the proviso that the reactant composition falls within the parallelogram J, F, G, and I.

- 9. The process of claim 5 within the proviso that the reactant composition falls Within the trapezoid I, G, B, and H.

. 10. The process of claim 5 with the proviso that the reactant composition falls within the triangle H, B, A.

11. A process for breaking petroleum emulsions of the water-in-oil' type characterized by subjecting the emulsion to a demulsifying agent including a cogeneric mixture of a homologous series of glycol ethers. of acyclic diglycerol; said cogeneric mixture being derived exclusively from acyclic diglycerol, ethylene oxide and butylene oxide in such weight proportions so the average composition of said cogeneric mixture, stated in terms of initial reactants, lies approximately Within the S-Sided figure of the accompanying drawing in which the minwhich 5-sided figure is identified by the fact that its area lies Within the straight lines connecting A, B, C, -D,

and H; with the proviso that the, hydrophile properties of said cogeneric mixture in an equal weight of xylene are sufiicient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

12. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst.

13. The process of claim 11 withthe proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first.

14. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide is substantially free from isobutylene oxide.

15. The process of claim 11 with the proviso that oxyalkylation takes place in presence of an alkaline catalyst and that the butylene oxide be added first, and with the further proviso that the butylene oxide consists of or more of the 1,2-isomer and approximately 15% or less 'of the 2,3:isomeric form, and is substantially free from isobutylene oxide.

16. The process of claim 15 with the proviso that the reactant composition falls Within the triangular area defined by C, D, and E.

17. The process of claim 15 with the proviso that the reactant composition falls within the parallelogram D, E, F, and J.

18. The process of claim 15 with the proviso that the reactant composition falls within the parallelogram J, F, G, and I.

19. The process of claim 15 with the proviso that the reactant composition falls within the trapezoid I, G, B, and H.

20. The process of claim 15 with the proviso that the reactant. composition falls within the triangle H, B, A.

References Cited in the file of this patent UNITED STATES PATENTS 2,507,910 Keiser et a1. May 16, 1950 2,552,528 De Groote May 15, 1951 2,574,544 De Groote Nov. 13, 1951 2,617,830 Kosmin Nov. 11, 1952 2,624,766 Butler Jan. 6, 1953 2,662,859 Kirkpatrick Dec. 15, 1953 2,677,700 Jackson et al May 4, 1954 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BY SUBJECTING THE EMULSION TO A DEMULSIFYING AGENT INCLUDING A COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOL ETHERS OF ACYCLIC DIGLYCEROL, SAID COGENERIC MIXTURE BEING DERIVED EXCLUSIVELY FROM ACYCLIC DIGLYCEROL, ETHYLENE OCIDE AND BUTYLENE OXIDE IN SUCH WEIGHT PROPORTIONS SO THE AVERAGE COMPOSITION OF SAID COGENERIC MIXTURE, STATED IN TERMS OF INITIAL REACTANTS, LIED APPROXIMATELY WITHIN THE 5-SIDED FIGURE OF THE ACCOMPANYING DRAWING IN WHICH THE MINIMUM ACYLIC DIGLYCEROL CONTENT IS AT LEAST 1.5% AND WHICH 5-SIDED FIGURE IS IDENTIFIED BY THE FACT THAT ITS AREA LIES WITHIN THE STRAIGHT LINES CONNECTING A,B,C,D, AND H. 